The crystal structures of naturally occurring and as-synthesized zeolitic aluminosilicates are composed of AlO.sub.4.sup.- and SiO.sub.4 tetrahedra which are crosslinked by the sharing of oxygen atoms. The term AlO.sub.4.sup.-, SiO.sub.4 and the like, are used to depict the tetrahedral atoms Al, Si and others, in four-fold coordination with oxygen, within the framework of the zeolite. It is understood that each of the four oxygen atoms thus depicted is linked to an additional tetrahedral atom, thus completing the charge requirements placed on each tetrahedral unit. The electrovalence of each tetrahedron containing an aluminum atom is balanced by association with a cation. Most commonly this cation is a metal cation such as Na.sup.+ or K.sup.+ but organic species such as quaternary ammonium ions are also employed in zeolite synthesis and in some instances appear as cations in the synthesized product zeolite. In general the metal cations are, to a considerable extent at least, replaceable with other cations including H.sup.+ and NH.sub.4.sup.+. In many instances the organic cation species are too large to pass through the pore system of the zeolite and hence cannot be directly replaced by ion exchange techniques. Thermal treatments can reduce these organic cations to H.sup.+ or NH.sub.4.sup.+ cations which can be directly ion-exchanged. Thermal treatment of the H.sup.+ or NH.sub.4.sup.+ cationic forms of the zeolites can result in the substantial removal of these cations from their normal association with the AlO.sub.4.sup.- tetrahedra thereby creating an electrovalent imbalance in the zeolite structure which must be accompanied by structural rearrangements to restore the electrovalent balance. Commonly when AlO.sub.4.sup.- tetrahedra constitute about 40% or more of the total framework tetrahedra, the necessary structural rearrangements cannot be accommodated and the crystal structure collapses. In more siliceous zeolites, the structural integrity is substantially maintained but the resulting "decationized" form has certain significantly different properties from its fully cationized precursor.
The relative instability of aluminum in zeolites, particularly in the non-metallic cationic or the decationized form, is well recognized in the art. For example, in U.S. Pat. No. 3,640,681, issued to P. E. Pickert on Feb. 3, 1972, there is disclosed a process for extracting framework aluminum from zeolites which involves dehydroxylating a partially cation deficient form of the zeolite and then contacting it with acetylacetone or a metal derivative thereof to chelate and solubilize aluminum atoms. Ethylenediaminetetraacetic acid has been proposed as an extractant for extracting aluminum from a zeolite framework in a process which is in some respects similar to the Pickert process. It is also known that calcining the H.sup.+ or NH.sub.4.sup.+ cation forms of zeolites such as zeolite Y in an environment of water vapor, either extraneous or derived from dehydroxylation of the zeolite itself, is effective in removing framework aluminum by hydrolysis. Evidence of this phenomenon is set forth in U.S. Pat. No. 3,506,400, issued Apr. 14, 1970 to P. E. Eberly, Jr. et al.; U.S. Pat. No. 3,493,519, issued Feb. 3, 1970 to G. T. Kerr et al.; and U.S. Pat. No. 3,513,108, issued May 19, 1970 to G. T. Kerr. In those instances in which the crystal structure of the product composition is retained after the rigorous hydrothermal treatment infrared analysis indicated the presence of substantial hydroxyl groups exhibiting a stretching frequency in the area of about 3740, 3640 and 3550 cm.sup.-1. The infrared analytical data of U.S. Pat. No. 3,506,400 is especially instructive in this regard. An explanation of the mechanism of the creation of these hydroxyl groups is provided by Kerr et al. in U.S. Pat. No. 3,493,519, wherein the patentees state that the aluminum atoms in the lattice framework of hydrogen zeolites can react with water resulting in the removal of aluminum from the lattice in accordance with the following equation: ##STR1##
The aluminum removed from its original lattice position is capable of further reaction with cationic hydrogen, according to Kerr et al. to yield aluminum-containing i.e., hydroxoaluminum, cations by the equation: ##STR2##
It has been suggested by Breck, D. W. and Skeels, G. W., "Zeolite Chemistry II. The Role of Aluminum in the Hydrothermal Treatment of Ammonium-Exchanged Zeolite Y, Stabilization", Molecular Sieves - II, A. C. S. Symposium Series 40, pages 271 to 280 (1977), that stabilization of NH.sub.4 Y occurs through hydrolysis of sufficient framework aluminum to form stable clusters of these hydroxoaluminum cations within the sodalite cages, thereby holding the zeolite structure together while the framework anneals itself through the migration of some of the framework silicon atoms.
It is alleged in U.S. Pat. No. 3,594,331, issued Jul. 20, 1971 to C. H. Elliott, that fluoride ions in aqueous media, particularly under conditions in which the pH is less than about 7, are quite effective in extracting framework aluminum from zeolite lattices, and in fact when the fluoride concentration exceeds about 15 grams active fluoride per 10,000 grams of zeolite, destruction of the crystal lattice by the direct attack on the framework silicon as well as on the framework aluminum can result. A fluoride treatment of this type using from 2 to 22 grams of available fluoride per 10,000 grams of zeolite (anhydrous) in which the fluorine is provided by ammonium fluorosilicate is also described therein. The treatment is carried out for the purpose of improving the thermal stability of the zeolite. It is theorized by the patentee that the fluoride in some manner becomes attached to the constructional alkali metal oxide, thereby reducing the fluxing action of the basic structural Na.sub.2 O which would otherwise result in the collapse of the crystal structure. Such treatment within the constraints of the patent disclosure has no effect on either the overall silicon content of the zeolite product or the silicon content of a unit cell of the zeolite.
Since stability is quite obviously, in part at least, a function of the Al.sub.2 O.sub.3 content of the zeolite framework, it would appear to be advantageous to obtain zeolites having lower proportions of Al.sub.2 O.sub.3 while avoiding the structural changes inherent in framework aluminum extraction. Despite considerable effort in this regard, however, only very modest success has been achieved, and this has applied to a few individual species only.
A process for increasing the SiO.sub.2 /Al.sub.2 O.sub.3 ratio in zeolites is disclosed in: commonly assigned U.S. Pat. No. 4,503,023, issue date Mar. 5, 1985, commonly assigned U.S. Pat. No. 4,610,856, issue date Sep. 9, 1986, U.S. Pat. No. 4,711,770, issue date Dec. 8, 1987 (U.S. patent application Ser. No. 880,103, filed Jun. 30, 1986), and in Skeels, G. W. and Breck, D. W. "Proceedings of the Sixth International Zeolite Conference", edited by David Olson and Attilio Bisio, Butterworth & Co. Ltd., pages 87 to 96 (1984). The process disclosed therein comprises inserting silicon atoms as SiO.sub.4 tetrahedra into the crystal lattice of an aluminosilicate having a SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio of at least 3 and pore diameters of at least 3 Angstroms with a fluoro- silicate salt in an amount of at least 0.0075 moles per 100 grams of the zeolitic aluminosilicate on an anhydrous basis, said fluorosilicate salt being in the form of an aqueous solution having a pH value within the range of 3 to about 7 and brought into contact with the zeolitic aluminosilicate at a rate sufficiently slow to preserve at least 60 percent of the crystallinity of the starting zeolitic aluminosilicate.
Commonly assigned European Patent Application Serial No. 85,902,354.1 describes ammonium fluoride salts of the metal cations iron and/or titanium which are used to treat the zeolites in an aqueous medium. Framework aluminum is complexed by the fluoride and removed from the zeolite. The metal cation is inserted into the framework in place of the aluminum.
Various attempts have been made to substitute chromium or tin into a zeolite framework via primary synthesis methods but none have been truly successful so far. Attempts to synthesize zeolites of the pentasil family of zeolites (ZSM-5 like) with a number of ions other than aluminum have been made. In some cases chromium or tin is found with the zeolite but not in the framework of the zeolite. The likelihood that either chromium or tin is not a part of the zeolite framework in primary synthesis products rests on the fact that such a high pH is required for synthesis that it is probable that the chromium or tin are present as oxides and/or hydrous oxides. For example, in U.S. Pat. No. 4,405,502 (Klotz) discloses the presence of up to 12.40 weight percent of Cr.sub.2 O.sub.3 with the crystalline chromosilicate (Example IV), but the Cr.sub.2 O.sub.3 in the product is present as amorphous or crystalline oxides. The examples teach that the chromium, initially dissolved in water, is rapidly precipitated as the hydroxide before ever coming in contact with the silica source. Further, "these results show that as the chromium factor became larger, more and more Cr.sub.2 O.sub.3 was detected in the product." (Column 24, lines 15-17.)
Marosi et al., in German Patent No. 2,831,630, disclose the presence of between 0.50 weight percent and 3.00 weight percent of Cr.sub.2 O.sub.3 with a ZSM-5 type structure. The amount of chromium that would be included in the framework of the ZSM-5, if indeed it were located therein, would range from 0.4 to 2.5 atoms out of 100 framework tetrahedral atoms. In the only Example where a product composition is given (1), the solid product would contain only 0.7 Cr atoms out of 100 in the framework, a value less than the compositions of the present invention. In Example 2 of U.K. Patent Application GB 2,024,790, (Taramasso et al.), a 6.00 weight percent of Cr.sub.2 O.sub.3 with a ZSM-5 type structure was obtained and which was designated "TRS-28". While the claims teach that the chromium atoms either, "entered the crystalline lattice in place of silicon atoms" or "in the form of salts of bisilicic or polysilicic acids", the evidence presented in the examples fairly teach that the chromium is not within the lattice framework of the ZSM-5 product. Surface areas of all of the products of the invention are given which indicate that there is a substantial reduction relative to a typical ZSM-5. This is evidence of some amorphous or dense phase present with the zeolite. Typically ZSM-5 or its' more siliceous analog silicalite will have a surface area, (BET), of greater than 400 square meters per gram. The chromium containing product of the U.K. Patent Application GB 2,024,790, had a surface area (BET) of 380 square meters per gram, a value at least 5% less than what might be expected of a pure zeolite sample. Additionally, the chromium containing product of said invention containing 6.0 weight percent Cr.sub.2 O.sub.3 would be expected to have an ion exchange capacity of 0.79 meq/gram, providing all of the chromium atoms were to be positioned in the framework in tetrahedral coordination with four oxygen atoms. However, only 0.0058 meq/gram of cations were actually found in the calcined (550.degree. C.) product, a value at least two orders of magnitude less than what would be necessary to balance the framework negative charges, if chromium were indeed in the framework. In order for chromium to be in the framework in tetrahedral coordination with four oxygen atoms, it is a requirement that there be present a positively charged species or cation in order to balance the negative charge caused by the presence of the trivalent chromium ion sharing the negative charges on four separate oxygen atoms with silicon. Lacking the cation, it is not possible for the chromium to be tetrahedrally coordinated with oxygen in this way and hence, the chromium of this example is not in the framework of the zeolite synthesized in the example. The converse is not necessarily true, namely, that if a positively charged cation is found to balance the negative charge on the chromium to satisfy the requirement of tetrahedral coordination with oxygen, that the chromium is in the framework. It would be evident that the chromium is in tetrahedral coordination with oxygen, but it does not necessarily prove that the chromium is located in the zeolite framework. It is probable that, like amorphous alumino-silicates, the amorphous chromosilicates can have tetrahedrally coordinated chromium atoms and hence ion exchange capacity.
European Patent Application 13,630 (Rubin et al.) discloses the presence of between 0.63 weight percent and 2.90 weight percent of Cr.sub.2 O.sub.3 with a ZSM-12 type structure. The samples described in the Tables of the patent application, particularly the products containing chromium, show a substantial loss of surface area. This indicates that the purity of the as-synthesized products is questionable and that they must contain amorphous material. A relative relationship can also be found in the Tables, namely that as the chromium content of the synthesis product increases, the reported X-ray crystallinity decreases.
In European Patent Application 14,059 (Rubin et al.) between 0.09 weight percent and 1.26 weight percent of Cr.sub.2 O.sub.3 with a ZSM-11 type structure was obtained. Similar observations can be made with these products; that the products containing chromium have reduced X-ray crystallinity, substantially reduced adsorption capacity for n-hexane and cyclohexane and substantially lower surface areas when compared to a product which does not contain chromium. Each observation taken alone would not preclude the incorporation of chromium in the ZSM-11 framework. However, taken together, these data are substantive evidence for the precipitation of an amorphous chromium containing phase with the zeolite, which under the very basic synthesis conditions employed is the expected result.
Dwyer et al. in U.S. Pat. No. 3,941,871 disclose the presence of tin in place of or as part of the organic template in a ZSM-5 type of a structure but not as a part of the ZSM-5 framework structure itself. In U.S. Pat. No. 4,329,328 (McAnespic et al.) the synthesis of a stannosilicate is suggested, but no examples of such synthesis are given nor are any properties of such materials suggested.
The above-mentioned references, while they may suggest the incorporation of the chromium or tin metal ions into the frameworks of the respective zeolites, provide consistent evidence that the metal ions are not included in the framework, and are merely precipitated with the zeolite as some other probably amorphous phase during the course of the synthesis process. Tielen et al. in "Proceedings of the International Symposium on Zeolite Catalysis", Siofok, Hungary, May 13, 1985, commented on isomorphic substitution in zeolites, stating that, "Generally speaking these new materials are claimed based upon their novel chemical composition or XRD spectrum or both. This novelty does not necessarily mean that the new materials contain the new element, or at least part of it, substituted in the zeolite framework. As far as we are aware, only in the case of boron substitution sound proof is available for its presence in the zeolite lattice." The reason for this failure is then obvious, since the very synthesis conditions used to synthesize the zeolite products are such that a nearly insoluble metal hydroxide precipitates thereby limiting the ability of the metal oxide to incorporate into the silicate units during crystal growth. This feature was only recently pointed out by Szostak et al. in Journal of Chemical Society, Faraday Trans. I. page 83 (1987). By recognizing the critical nature of the pH they were able to, for the first time, synthesize the ferrisilicate analog of ZSM-5.
It should be further pointed out that Tielen at the top of page 9 states "based on this table and the evidence mentioned in the introduction, elements with ionic radii between 0.020 and 0.061 are potential candidates for incorporation into a framework . . . " Using the values given for the Shannon references (radii in tetrahedral coordination) it is observed that Sn.sup.+4 has an ionic radius of 0.069 nm or 0.69 .ANG. (note that Shannon reports this value as the crystal radii) which is outside the range stipulated by Tielen and thus would not be expected to be in the framework. Although values for Cr.sup.+3 and Sn.sup.+2 are not provided in Tielen, they are provided by R. D. Shannon in his original paper (Acta Cryst. A 32, 751-767 (1976)) as Cr.sup.+3 =0.755 and Sn.sup.+2 =1.36. It should be noted that the values for Cr.sup.+3 and Sn.sup.+2 are for octahedral coordination and the number for tetrahedral coordination would be expected to be smaller. Further, the numbers presented by Tielen are the crystal radii (see Shannon Table 1, page 752). Accordingly, none of these metal ions would be expected to be in the framework.
Another reference which has been cited in this art is Canadian Patent No. 1,127,134 to Morrison. This reference discloses an "alumino-silicate zeolite" which contains a metal oxide selected from the group consisting of indium, boron, ruthenium, platinum, chromium, rare earth, vanadium, palladium, molybdenum, mercury, tellurium, silver and mixtures thereof. However, there is no mention or hint that these metals are or could be in the framework. Indeed, on page 6, lines 1-7, the patentees state that it is not known whether the metal is present as a metal or as a metal compound. Given this uncertainty, it would be pure speculation to state that Morrison discloses an aluminosilicate zeolite where some of the aluminum in the framework has been replaced by chromium or some other metal. Accordingly, there is nothing in Morrison that suggests a zeolite having chromium as a framework metal.
Two other references which deal with novel structures and methods of preparation of zeolites and mention chromium in passing are U.S. Pat. No. 4,581,212 (Araya) and U.S. Pat. No. 4,420,467 (Whittam). Although both references include chromium in a long list of elements that allegedly can be incorporated into the framework, we have reproduced their preparation and have determined that chromium is not in the framework (see Examples 26 and 27).
The above mentioned references do suggest that it is desirable to synthesize zeolites or molecular sieves containing chromium or tin in the framework tetrahedral sites. However the methods employed in the references leave little doubt that the metal has been deposited with the zeolite either as an oxide or hydroxide or as an amorphous metal silicate. The references further demonstrate the difficulty involved in the incorporation of these metal ions in the zeolite tetrahedral framework positions. The uniqueness of the method of the current application which relies on the solubility of the chromium and tin metal ions in an acidic medium, and the Secondary Synthesis procedure to incorporate the metal ions into the framework is further demonstrated. As for the obviousness of the Secondary Synthesis procedure to incorporate any metal ion into the framework of an existing zeolite, all attempts to use this process with the ions of phosphorus or boron have thus far been unsuccessful. Boron is the only metal ion thus far that has been successfully incorporated into the pentasil zeolite framework via primary synthesis methods (Tielen et al.). Only by careful control of the Secondary Synthesis conditions can one be successful in incorporating iron and/or titanium (D-13733), or chromium and/or tin into the framework of existing zeolites or molecular sieves.
Secondary Synthesis as used herein means a process whereby a molecular sieve product is treated by some method (Secondary Synthesis) to obtain a molecular sieve product that is either not obtainable by primary synthesis methods or is prepared with great difficulty or is not normally found in nature.
The present invention relates to novel zeolite compositions which contain significant framework tetrahedral atoms, which are not found to any significant level either in naturally occurring zeolites or in synthetic zeolites.
In the present invention, zeolite Y, zeolite L, mordenite and zeolite LZ-202 (an omega type zeolite prepared without the use of a templating agent as disclosed in U.S. Pat. No. 4,840,779) are treated with aqueous ammonium fluoride salts of either or both chromium or tin. During the treatment aluminum is removed from the molecular sieve framework and the metal ion is incorporated therein. By means of this invention, the metal ions of chromium and/or tin can be incorporated into molecular sieve frameworks where they are not normally found in nature.